Novel carbon-carbon bond-forming reactions using carbocations produced from substituted propargyl silyl ethers by the action of TMSOTf
Novel carbon-carbon bond-forming reactions using carbocations produced from substituted propargyl silyl ethers by the action of TMSOTf
复制标题
DOI：
10.1021/jo010157p
复制
发表时间：
2001-06-29
影响因子：
3.6
通讯作者：
Saito, S
中科院分区：
文献类型：
--
作者：
Ishikawa, T;Okano, M;Saito, S
使用稳定的烯丙基、炔丙基或烯丙基-炔丙基杂化阳离子已开发出非常有用的碳-碳键形成反应。这些碳正离子可由硅基1(PI供体)取代的丙烯基醚在-78℃的二氯甲烷中与三甲基硅基三氟甲磺酸反应生成，并可被富含电子的芳烃、烯丙基硅烷或烯醇硅醚进行亲核攻击，产生烯、炔及其衍生物。还建立了一种利用烯丙基-炔丙基杂化阳离子进行区域和立体选择性合成共轭烯炔的新方法。
Highly useful carbon-carbon bond forming reactions using stable allenyl, propargyl, or allyl-propargyl hybrid cations have been developed. These carbocations could be generated from silyl 1-(pi -donor)-substituted propargyl ethers by the action of trimethylsilyl trifluoromethanesulfonate in dichloromethane at -78 degreesC to room temperature and could be attacked nucleophilically by electron rich arenes, allylsilanes, or enol silyl ethers, giving rise to allenes, alkynes, and their derivatives. A novel method for regio- and stereoselective synthesis of conjugated enynes utilizing allyl-propargyl hybrid cations has also been established.